Chemical reactions



Dec. 18, 1945. c, w. 'T'YsoN CHEMICAL REACTIONS Filed Jne 15, 194s l m NQ @Q lll um.. wvmrlrm Patented ec.l 18, 1945 vCHEMICAL REACTIONS Charles W. Tyson, Summit, N. `J., assignor to Standard Oil Development Company, a corporationv of Delaware v Application June 15, 1943, Serial No. 490,831

.'7 Claims.

This invention relates to treating hydrocarbon fluids, and more particularly, relates to starting up the operation of a cracking or conversion unit using powdered catalyst.l

When it is desired to start the operation oi a conversion process using powdered catalyst, the whole unit is at atmospheric temperature. The conversion and regeneration of catalyst take place 4at relatively high temperatures and the whole to two days time to prepare fit for the cracking Where powdered catalyst or conversion process. is used, it is essential to have the whole system or unit heated up to above the condensation point of water before the powdered catalyst is intro f duced into the system to prevent agglomeration of the catalyst particles, plugging, etc.

According to my invention, heated air is -iirst passed through the whole system, including the reaction side and regeneration side, until it is at a temperature of about 225 to 400 F. An auxiliaryvburner is then started andthe supply oiheated air to the regeneration side is replaced byhot combustion gases diluted with air. About this time the air going to the reaction side is replaced by superheated steam..

Then combustion gases from the auxiliary burner at 'a temperature of about 1250 F. are quenched' with the cold catalyst which is then supplied to the regenerator side of the unit. 1 In this way the cold catalyst is heated up quickly and heatis also supplied throughout the equipment. y

The compressor used for supplying air` during regeneration when the plant is operated for cracking oil is used for forcing hot air to the system during starting up and air to the auxiliary burner for supplying hot gases when the supply of hot air from the superheater is shutoi. The superg heater furnace used for heating the oil vapors to the reaction temperature during the cracking or conversion operation is used during starting up erated catalyst hopperA I6. A Cottrell precipi- `tator I8 is also associated with the regenerated catalyst hopper.

The spent catalyst hopper I2 has a standpipe 22 provided with a control valve 24l for controlling the amount of spent catalyst passing through-line 26 to the regeneration zone I4 during the use of the unit as a cracking and regenerating unit.

The regeneration zone I4 is provided with a bottom distribution plate 28. K The regenerated catalyst` hopper I 6 is provided with a standpipe 32 having a control valve 34 for controlling `the amount of regenerated catalyst passing through line 36 to the reaction zone I0 during the operaA tion of the unit for converting hydrocarbons. The reaction zone I0 is lprovided with a bottom distribution lplate 3.8.

The Cottrell 'precipitator' I8 is provided with a standpipe 42 having a control valve 44. 'Staudpipe 42 communicates with line 46 which leads to a cyclone separator 48 which has a return pipe 52 for conducting separated catalyst particles'to the regenerated catalyst hopper I6.

The regeneration zone I4 has a top outlet line 54 which leads to the cyclone separator 48. Preferably more than one cyclone separator is use d,

and other forms of separating means may be used;

for heating air and `later steam for preheating the whole unit,

In the drawing, the iigure represents one form of apparatus which may be used in carrying out my invention.

yReferring now to the drawing, the reference The separated gas from the cyclone separator 48 passes through line 56 through a cooler 58 and4 then to the Cottrell precipitator I8. The Cottrell precipitator I8 has a top' outlet line 62.

The regenerated catalyst hopper has a second y standpipe 12 which branches intor a bypass line I4 and al recycle line 1.6. The bypass standpipe 4'IIl has a control valve 82. The recycle standpipe 'I6 has a control valve 84. 'I'he recycle line 8@ connected with the recycle standpipe I6 is pro' videdV with a heat exchanger 88 for cooling regenerated catalyst being passed to the regeneration zone I [during operation of the unit for conversionl of hydrocarbons tocontrol the temperature of theI catalyst particles undergoing re generation.

During use of the whole unit for cracking and regeneration, air is used for conveying the cata@l lyst particles on the regeneration side andsuper heated steam. and/or oil vapors are used for under pressure. This compressor or blower- 92 is used for passing the hot air through'thesystemwhen the system is being started up.

A superheater furnace shown at 94 is used .for-: heating oil vapors to the desired reaction tem-- perature when the unit is being used for coi'ivertfl ing hydrocarbons. During starting up the superheater furnace is used for superheating air or later steam, which is used for conveying regenerated catalyst to the reaction zone I0.

With the whole system or unit at substantially atmospheric temperature, the starting up procedure forming my invention will now be described. The air line 96 which normally has a continuation 98 and a valve |02 for conducting spent catalyst from the bottom of the standpipe 22 to the regeneration zone I4 is used for conducting air under pressure from the compressor 92. The valve |02 is closed and valve |04 in branch line |06 is opened so-that air under pressure passes through line |08 and superheater furnace 94. The air is heated to a temperature of about 1000 F. and is passed through the various parts of the equipment as will be presently described. The valve 24 in standpipe 22, valve 34 in regenerated catalyst standpipe 32, valve 84 in recycle standpipe 16 and valve .82 in bypass standpipe 18 are closed and valve 44 in the precipitatorlstandpipe 42 is left open.

The heated air leaves the superheater through line I |2 having valve I I4. A portion of the heated air is passed through branch line ||6 having valve H8 into line 26 below the valve 24 and the heated air is introduced into the bottom of the regeneration zone I4. The hot air passes through the outlet 54 to the cyclone separator 48.

The standpipe 32 is provided with a valved discharge line |22 for permitting escape of heated air in order to insure heating of the standpipe. Standpipe 'I6 has a valved discharge line |24 and bypass standpipe 18 has a valved discharge line |26. 'Ihese discharge lines are located above the closed control valves 34, 84 and 82 in the respective standpipes. By opening valves |22, |24 and |26, hot air may be directed into the regenerated catalyst hopper v I6 and into the standpipes 32, 16 and 18 to heat these parts of the system to the desired temperature.

Another portion of the hot air is passed through lin-e |32 and branch line |34 into the line 46 below the opened valve 44 in the precipitator hopper standpipe 42. One portion oi' the heated air passes through line 46 to the cyclone separator 48 and another portion up standpipe 42, thus heating both the standpipe and return line. Hot air from the cyclone separator passes through line 56 and upwardly through the Cottrell precipitator I8.

Another portion of the heated air passing through line |32 is passed throughline |36 and into the regenerated catalyst recycle line 86 below the control valve 84 in standpipe 16. This heated air also passes into the bottom portion of the regeneration zone I4.

Another portion of the hot airvafter leaving the superheater furnace 94 through line ||2 is passed through line 38 and bypass line |42 having a valve |44 for conducting the hot air through the bottom portion of the regenerated catalyst bypass standpipe 18 and into line 14 which leads' into the bottom portion of thev regeneration zone'l4.

Another portion of the heated air passes through branch line |46 which communicatesv with line I I2 from the superheater furnace 94 ahead of the valve lI |4 in line 2. `Line |46 h a valve |48. Line |46 conducts hot air to the bottom of vstandpipe 32 below control valve 34 and passes through line 36 to the bottom portion of the reaction zone I0. The hot air leaves the top of the reaction zone through line |52 and passes into a cyclone separator |54 having a return pipe |56 leading into the spent catalyst hopper I2. Preferably more than one cyclone separator is used and other forms of separating means may be used. The cyclone separator |64 has an outlet line |58 and a valve |62. By con- 1 F. or higher. At this point the further heating on the regeneration side is accomplished by an auxiliary burner |12 which has a feed inlet |14 at the top for introducing gaseous fuel or any other suitable fuel. The auxiliary burner has an outlet; |16. The line |16 communicates with line |42 above described but the valves separate'these systems as will be presently described.

Compressed air from line 96 is passed through manifold |82 into the auxiliary burner |12 through line |84 as primary air. Secondary air from line |82 is passed through line |86 to reduce the temperature of the combustion gases to from about 1000 F.-l250 F.

With the auxiliary burner in operation, the supply of air to the superheater furnace 94 is cut oli by closing valve |04, and valve I|4 in outlet line ||2 is also closed. Steam is passed through line |88 into' line |08 and superheater furnace 94 for superheating the steam to about 1000 F. Thelsuperheated steam is withdrawn through line |46 and into line 36. The superheated steam has now replaced the hot air passing through line 36 to the reaction side of the apparatus.

Returning now to the auxiliary burner which produces combustion gases at a temperature of about 1000 F., with the valve I4 in line |I2 closed, hot, combustion gases and excess air now replace the hot air first used on the regeneration side of the apparatus.

Steam is passed through the reaction side of the apparatus at such a rate that the temperature goes up slowly and the heating is continued until the reaction'side is at a temperature of about 800 to 900 F.

'I'he system is now ready for the introduction of catalyst and as the catalyst is at a relatively low temperature or at room temperature, it is necessary to supply additional heat to the part of the unit into which the cold catalyst is being introduced. Preferably the cold catalyst is introduced into regenerated catalyst bypass line 14 through line |92. 'I'he hot combustion gases being introduced into line 14 have their temperature increased in the following manner. The secondary air passing to the auxiliary burner through line |86 is reduced in relation to the amount of fuel ilred so that the combustion gases leaving the burner through line |16 are at 'a temperature of about 12.50 F.

These combustion gases at a temperature of about-1250 F. are then passed through line |42 and mixed with the cold catalyst, the mixture being passed through the bypass line 14 to the regeneration zone I4.l The rest of the combustion gases from the auxiliary burner are passedv through line |38 after being mixed with coxn' pressed air passing through line |94 having a valve |96. This air is fed from theline |82 and a suiiicient amount of air is added to reduce the temperature of the combustion gases to about 1000 F. 'I'he fresh unused catalyst contains moisture and by preheating it in this way, excess troduced into the system may be circulated through the regenerator I4 and the regenerated catalyst hopper I 6 through standpipes '|2`, 16 and 18 and cyclone separator-48 which returns the catalyst to the regenerated catalyst hopper. Before circulating the catalyst, it is, ofcourse, necessai-y to open control valves 84 and 82 While at `the same time closing discharge lines I2 4and After the system has become` heated up, valved discharge lines |22 and |84 are preferably closed. By circulating the catalyst in this way, the catalyst in the regenerated catalyst hopper is maintained hot. However, the circulation should not be too great as the heat loss is greater due to.

the higher temperatureofthe gases leaving the cyclone separator 48. After about 60% or more of the catalyst has been introduced and if the temperature of the catalyst is not less than 400 Vfor acid-treated natural clays and about 600 F.

branch through line |42 so that atmospheric air under-pressure is used on the regeneration side of the unit.

As above stated, when the auxiliary burner is turned off, heating oil is supplied to the regeneration zone I4. This oil may be any cheap combustible oil, such as gas oil, or may be any other hydrocarbon oil. 'I'he oil is passed through line 208 into the bottom portion of the regeneration zone I4 which now contains powdered catalyst. The regenerationzone'is at a temperature of about 900 to 1000 F. andas there is sumcient air present, the oil burns and supplies heat to the catalyst in the regeneration zone. The catalyst is heated to about 1000 to 1050 F.'whilst circulating it between the regenerated catalyst hopper I6 and the regenerator I4, and all of the catalystl is raised to about this temperature After this the unit is'now ready for introducing hot catalyst to the reaction zone I8, and control valve 34 in standpipe 32 is opened to permit the'ilow of catalyst into line 36. Steam continues to flow through line |46 and the mixture in line 38 is a mixture of steam and catalyst which is passed into the reaction zone I0. Further amounts of cold catalyst are introduced into the bypass line 'I4 to make up for the heated catalyst being passed to the reaction zone.

This procedure is continued until the spent catalyst hopper I2 becomes substantially illed with hot catalyst. 'I'he control valve 24 vin standpipe. 22 is then opened to permit circulation of catalyst from the spent catalyst hopper I2 to the regeneration zone I4. When all of the catalyst has been added, the further addition of cold catalyst through line |92 into vbypass line 14 is stopped. The catalyst is then slowly circulated through the, *whole system to get the whole system at about-a uniform temperature of 800 to 1000 F. When the circulation has been main.- tained for some time, the system is ready for 'the introduction of oil which is to be cracked, Passage of steam through line |88 may be continued or-discontinued as desired. The oil vapors from 'a ilash tower are passed through line 208 into line |08 and through the superheater furnace 94 for heating the oil vapors to a temperature of about 800 to 950 F. The heated oil vapors at reaction temperature are then passed through line |46 and to the bottom of the regenerated catalyst standpipe 32 where they are mixed with lthe catalyst and the mixture introduced into the reaction zone I0. n

After the catalyst particles pass through the lreaction zone, they are contaminated'with coke or carbonaceous material and they are then passed to the regeneration zone I4 where they are mixed with air and the carbonacecus deposit burned oil'. The regenerated catalyst is then accumulated in regenerated catalyst hopper I6. A portion of the regenerated catalyst is passed through .bypass line 14 to the regenerator I4 and another portion is cooled by passing through the recycle line 88 and heat exchanger 88 for controlling the temperature during regeneration.

Instead of passing oil vapors through 1ine,208 a reduced crude or other heavy oil may be heated in a vaporizer furnace, flashed in a flash tower and the vapors then taken overhead through line 208 to the superheater furnace 94. Instead of using vapors, liquid oils which contain non-vaporizable constituents, or if they are entirely vaporizable, may be preheated to a temperature of about to 600 F. and mixed asv liquids or liquid and vapor mixtures with the regenerated catalyst from line 32. The regenerated catalyst is at a sufl'lciently high temperature to vaporize the stock and also to supply the heat of reaction.

The standpipes and hoppers are preferably aerated.

While I have'shown a preferred form of my invention', it is to be understood that various changes and modications may be made without departing from the spirit of my invention.

I claim:

1. In a starting up procedure for a hydrocarbon conversion unit substantially at atmospheric temperature 'and using iiuidized powdered catalyst to be continuously circulated during the conversion process in a closed cycle through a reaction zone and a regeneration zone for the spent catalyst, the steps oi' passing heated air through the entire unit prior to the introduction of powdered catalyst until a temperature above about 225'F. is obtained for the entire unit,` then substituting superheated steam for air going to said reactionzone to displace the air and to prepare the reaction zone for hydrocarbon conversion and then adding powdered catalyst to said regeneration zone while continuing the heating with heated air.

2. In a, starting up procedure for a hydrocarbon conversion unit substantially at atmospheric temperature and using fluidized divided catalyst particles to be continuously circulated during the y conversion process in a closed cycle through a to the regeneration side and substituting steam for the remaining heated air going to the reaction "side, adding cold catalyst particles to said. regenfiuidized .powdered catalyst in a cycle through said zones and associated parts which comprises heating air to about 1000 F. and passing it through the entire system prior' to the introduction of powdered catalyst, continuing heating with air until the temperature at the outlets is over about 250 F., substituting superheated steam for the portion of the air going to the reaction side, introducing cold divided solid catalyst on the regeneration side and circulating it on this side until the catalyst particles are heated to about 600 F., adding combustible fuel to said regenerationzone to raise the`r temperature of the catalyst particles in said'regeneration zone to about 1000o Pfand then passing the catalyst particles to the reaction side and recycling the catalyst particles through the whole uni/t until the desired temperature is obtained.

4. A procedure as defined in claim 3 wherein the heated air on the regeneration side is replaced by hot freshly produced combustion gases and another portion of hotter freshly produced combustion gases is used for admixture with the cold catalyst particles on the regeneration side, the addition of combustion gases to said regeneration zone being discontinued when combustible fuel is added to said regeneration zone.

5. A starting-up procedure for heating up a reaction zone, a regeneration zone and associated parts substantially at atmospheric temperature and designed for the continuous circulation of fluidized powdered catalyst in a, cycle through said zones and associated parts which comprises heating air to about 1000 F. and passing it through the entire system prior to the introduction of powdered catalyst, continuing heating with air until the temperature at the outlets is over about 250 F., substituting superlleated steam for the portion of the air going to the reaction side, replacing the heated air on the regeneration side with hot combustion gases, introducing cold catalyston thev regeneration side and circulating it on this side until the catalyst is heated to about 60G-800 F., and using another portion of hotter combustion gases for admixture with the cold catalyst on the regeneration side for supplying additional heat to the unit.

6. A procedure according to claim 5 wherein the introduction of combustion gases is replaced by compressed atmospheric air on the regeneration side and oil vapors are introduced into said reaction zone to begin the continuous conversion operation followed by continuous regeneration of the spent catalyst particles.

7. In a starting-up procedure for a catalytic cracking plant substantially at atmospheric temperature and using iluidized powdered catalyst wherein a regeneration zone, regenerated catalyst standpipe and hopper, a bypass line between the regenerated catalyst hopper and regeneration zone, a reaction zone, a spent catalyst hopper and standpipe and associated parts are provided and wherein the powdered catalyst is to be continuously circulated during the conversion process in a cycle comprising said zones, hoppers and standpipes, the steps of passing air through a superheater furnace and passing the heated air through all parts of the plant until an outlet temperature of about 250 F. is obtained, replacing heated air on the regeneration side with freshly produced hot combustion gases from an auxiliary burner, replacing air passing through said superheater by steam and passing the superheated steam to the reaction side of the plant, adding cold catalyst to said regeneration zone, recirculating the catalyst between said regeneration zone and regenerated catalyst hopper, and then passing it to said reaction zone while continuing v addition of cold catalyst to said regeneration zone, adding further heat to said regeneration zone, replacing the combustion gases on the regeneration side with compressed atmospheric air and replacing the steam by oil vapors heated in said superheater furnace so that the plant is ready for a continuous cracking and regeneration operation.

CHARLES W. TYSON. 

